Patent GB-977232-A (GB)
Title: Novel dihydroxytetrahydropyran compounds, their preparation and use
IPC: C07H19/01
Filed: 1962-12-27
Abstract: The invention comprises dihydroxytetrahydropyran compounds of the general formula <FORM:0977232/C1/1> wherein each R represents a hydrogen atom or a C1 to C3 alkyl group and X represents -CHO, -CH2OH, -CO2H or -CO2R1, wherein R1 is a C1 to C18 saturated or olefinically unsaturated aliphatic hydrocarbyl group. They are prepared by the hydroxylation, preferably with hydrogen peroxide in the presence of tungstic acid, of a 3, 4 dihydro-1, 2-pyran of the general formula <FORM:0977232/C1/2> or by the conversion of one X group into another. The compounds of the invention may be polymerized by heating to form polyhemiacetals, i.e. a polymer of formula <FORM:0977232/C1/3> when X is -CHO, of formula <FORM:0977232/C1/4> when X is -CO2H, of formula <FORM:0977232/C1/5> when X is -CO2R1 and of the Formula V wherein the CO2R1 group is replaced by CH2OH when X is -CH2OH; x being an integer greater than one. If desired the above polymers can be cross-linked with, for example, polycarboxylic acids or polyisocyanates or, in the ester-containing polymer, through the peroxide-catalyzed polymerization of any unsaturated groups present in the R1 radical. The compounds of Formula I may also be:  (1) Hydrogenated; 1, 2, 5, 6 hexanetriols, when X is -CHO or -CH2OH, or 2, 5, 6 trihydroxyhexanoic acids, when X is -CO2H or -CO2R1, being formed. These polyols may then be reacted with aliphatic a -b mono-ethylenic aldehydes having a terminal methylene group to form 2-vinyl dioxolane compounds. The acrolein acetal of 2, 5, 6 trihydroxyhexanoic acid or an ester thereof may be esterified or transesterified with itself or, more preferably, with a diol.  (2) Converted into a cyclic acetal of the general formula <FORM:0977232/C1/6> by reaction with an aliphatic a -b mono-ethylenic aldehyde having a terminal methylene group; and  (3) linked together by, for example, the Tishchenko) reaction and the compounds so formed reacted with an aliphatic a -b  mono-ethylenic aldehyde having a terminal methylene group to form, for example, compounds of the formula <FORM:0977232/C1/7> The compounds may also be obtained by subjecting the cyclic acetal of the 6-carboxaldehydes of Formula I to the Tishchenko reaction or by esterifying or transesterifying the cyclic acetals of the 6-carboxylic acid or 6-carboxylic acid esters of Formula I with the 6-methanol compounds of Formula I.  The compounds of the invention or the cyclic acetals derived therefrom may be linked together by means of a polyfunctional compound reactive with the group X in the 6-position, e.g. aldol condensation products are formed by reacting compounds of Formula I wherein X is -CHO with a dialdehyde, polyesters are formed by reacting compounds of Formula I wherein X is -CO2H or -CO2R1 with a polyol or an ester thereof or by reacting compounds of Formula I wherein X is -CH2OH with a polycarboxylic acid or polyester thereof. Also mentioned are the higher fatty acid esters of 2, 3 -dihydroxtetrahydropyran-6-methanols and various metal salts and the ammonium salt of the 2, 3 dihydroxytetrahydropyran 6-carboxylic acids.  U.S.A. Specifications 2,479,283 and 2,479,284 are referred to.ALSO:Dihydroxytetrahydropyran compounds of the general formula <FORM:0977232/C3/1> wherein each R represents a hydrogen atom or a C1 to C3 alkyl group and X represents -CHO, -CH2OH, -CO2H or -CO2R1, wherein R1 is a C1 to C18 saturated or mono-olefinically unsaturated aliphatic hydrocarbyl group, are polymerized by heating to form a polymer of the formula <FORM:0977232/C3/2> when X is CHO, of formula <FORM:0977232/C3/3> when X is CO2H, of formula <FORM:0977232/C3/4> when X is CO2R1 and of Formula V wherein the CO2R1 group is replaced by CH2OH when X is CH2OH; x being an integer greater than one. These polymers may be cross-linked with, for example, polycarboxylic acids or polyisocyanates or, in the ester-containin polymer, through peroxide-catalyzed polymerization of any unsaturated groups in the R1 radical. Any of these polymers can be blended or otherwise combined with plasticizing materials; other polymers, e.g. epoxy resins, polyurethane resins, polyamides, urea-formaldehyde and phenol resins, polythiopolymercaptans or vinyl resins; coal tar; asphalt; middle oil and coal tar pitch. U.S.A. Specifications 2,479,283 and 2,479,284 are referred to.ALSO:Cloth or paper is coated with a solution of a polymer (a) of formula: <FORM:0977232/B1-B2/1>  (b) of formula: <FORM:0977232/B1-B2/2>  (c) of formula: <FORM:0977232/B1-B2/3> <FORM:0977232/B1-B2/4> (d) of Formula V wherein the COOR1 group is replaced by CH2OH, (e) is derived from (a), (b), (c) or (d) and a polycarboxylic acid or a polyisocyanate, or (f) obtained by the peroxide-catalyzed polymerization of any unsaturated groups present in R1 of (c) above.  In the formulae R represents a hydrogen atom or a C1-C3 alkyl group, R1 represents a C1-C18 saturated or olefinically unsaturated aliphatic hydrocarbyl group and x is an integer greater than 1.  U.S.A. Specifications 2,479,283 and 2,479,284 are referred to.ALSO:The copper salt of a carboxylic acid of the general formula <FORM:0977232/A5-A6/1> wherein R represents a hydrogen atom or a C1 to C3 alkyl group and X is - CO2H, may be used as a component of insecticidal and fungicidal compositions.  U.S.A. Specifications 2,479,283 and 2,479,284 are referred to.